Fluorinated compound, and fluoropolymer, process for its production and resist composition containing it

ABSTRACT

To provide a fluoropolymer having functional groups and having high transparency in a wide wavelength region, and a resist composition comprising the fluoropolymer. 
     A fluoropolymer (A) having monomer units formed by polymerization of a fluorinated diene represented by the following formula (1): 
       CF 2 ═CFCH 2 CH-Q-CH 2 CH═CH 2   (1) 
     wherein Q is (CH 2 ) a C(CF 3 ) 2 OR 4  (wherein a is an integer of from 0 to 3, R 4  is an alkyl group or a fluorinated alkyl group having at most 20 carbon atoms which may have an etheric oxygen atom, an alkoxycarbonyl group having at most 6 carbon atoms, or CH 2 R 5  (wherein R 5  is an alkoxycarbonyl group having at most 6 carbon atoms)), or (CH 2 ) d COOR 6  (wherein d is 0 or 1, and R 6  is a hydrogen atom, or an alkyl group or a fluorinated alkyl group having at most 20 carbon atoms), a process for its production and a resist composition having the fluoropolymer (A) as a base.

TECHNICAL FIELD

The present invention relates to a novel fluorinated compound, afluoropolymer and a process for its production, and a resistcomposition.

BACKGROUND ART

As fluoropolymers having functional groups, functional group-containingfluoropolymers are known which are used for fluorinated ion exchangemembranes, curable fluorinated resin coating materials, etc. However,they are all basically straight chained polymers, and they areobtainable by copolymerization of a fluoroolefin represented bytetrafluoroethylene with a monomer having a functional group.

Further, a polymer containing functional groups and having a fluorinatedalicyclic structure in its main chain, is also known. As a method forintroducing functional groups to the polymer having a fluorinatedalicyclic structure in its main chain, a method of utilizing terminalgroups of a polymer obtained by polymerization, a method of subjecting apolymer to high temperature treatment to oxidize and decompose sidechains or terminals of the polymer to form functional groups, or amethod of copolymerizing a monomer having a functional group, ifnecessary, by adding treatment such as hydrolysis to introducefunctional groups, is, for example, known (see Patent Documents 1, 2, 3and 4).

The above-mentioned methods are available as methods for introducingfunctional groups to a polymer having a fluorinated alicyclic structurein its main chain. However, the method for introducing functional groupsby treating the terminal groups of the polymer, has a drawback that thefunctional group concentration is low, and no adequate characteristicsof the functional groups can be obtained. Whereas, by the method forintroducing functional groups by copolymerizing a monomer having afunctional group, there will be a problem such that if the functionalgroup concentration is increased, the mechanical properties tend toDecrease due to a decrease of the glass transition temperature (Tg).

Patent Document 1: JP-A-4-189880

Patent Document 2: JP-A-4-226177

Patent Document 3: JP-A-6-220232

Patent Document 4: WO02/064648

DISCLOSURE OF THE INVENTION Problems that the Invention is to Solve

The present invention provides a fluorinated compound having highconcentration of functional groups and adequate characteristics of thefunctional groups and having high transparency in a wide wavelengthregion, a fluoropolymer and a process for its production. Further, thepresent invention provides a resist composition which can form achemical amplification type resist excellent particularly intransparency for far ultraviolet rays such as KrF or ArF excimer laseror vacuum ultraviolet rays such as F₂ excimer laser and dry etchingcharacteristics, and a resist pattern excellent in sensitivity,resolution, dissolution velocity, flatness and the like.

Means of Solving the Problems

The present invention is to solve the above problems, and has thefollowing gists.

(1) The present invention provides a fluoropolymer (A) having monomerunits formed by cyclopolymerization of a fluorinated diene containingfunctional groups represented by the following formula (1):

CF₂═CFCH₂CHQ-CH₂CR¹═CHR²  (1)

wherein each of R¹ and R² which are independent of each other, is ahydrogen atom or an alkyl group having at most 12 carbon atoms, Q is(CH₂)_(a)C(CF₃)_(b)(R³)_(c)OR⁴ (wherein a is an integer of from 0 to 3,b and c are integers of from 0 to 2 satisfying b+c=2, R³ is a hydrogenatom or a methyl group, R⁴ is an alkyl group or a fluorinated alkylgroup having at most 20 carbon atoms which may have an etheric oxygenatom, an alkoxycarbonyl group having at most 6 carbon atoms, or CH₂R⁵(wherein R⁵ is an alkoxycarbonyl group having at most 6 carbon atoms)),or (CH₂)_(d)COOR⁶ (wherein d is 0 or 1, and R⁶ is a hydrogen atom, or analkyl group or a fluorinated alkyl group having at most 20 carbonatoms).

(2) The present invention provides a method for producing afluoropolymer (A), characterized by cyclopolymerization of a fluorinateddiene containing functional groups represented by the above formula (1).

(3) The present invention provides a fluorinated diene represented bythe following formula (2) or (3):

CF₂═CFCH₂CH((CH₂)_(a)C(CF₃)_(b)(R³)_(c)OR⁴)—CH₂CH═CH₂  (2)

wherein a is an integer of from 0 to 3, b and c are integers of from 0to 2 satisfying b+c=2, R³ is a hydrogen atom or a methyl group, R⁴ is analkyl group or a fluorinated alkyl group having at most 20 carbon atomswhich may have an etheric oxygen atom, an alkoxycarbonyl group having atmost 6 carbon atoms or CH₂R⁵ (wherein R⁵ is an alkoxycarbonyl grouphaving at most 6 carbon atoms),

CF₂═CFCH₂CH((CH₂)_(d)COOR⁶)—CH₂CH═CH₂  (3)

wherein d is 0 or 1, and R⁶ is a hydrogen atom, or an alkyl group or afluorinated alkyl group having at most 20 carbon atoms.

(4) The present invention provides a resist composition characterized bycomprising the above fluoropolymer (A), an acid-generating compound (B)which generates an acid under irradiation with light, and an organicsolvent (C).

EFFECT OF THE INVENTION

According to the present invention, it is possible to produce afluoropolymer having an alicyclic structure in its main chain and havingfunctional groups in its side chains. The fluoropolymer (A) obtained bythe present invention has high chemical stability and heat resistance.Yet, functional groups are introduced in the side chains, whereby it ispossible to exhibit sufficient characteristics of functional groupswithout bringing about a decrease of Tg, which used to be difficult toaccomplish with conventional fluoropolymers. Further, such afluoropolymer (A) has high transparency in a wide wavelength region. Theresist composition of the present invention can be used as a chemicalamplification type resist excellent particularly in transparency for farultraviolet rays such as KrF or ArF excimer laser or vacuum ultravioletrays such as F² excimer laser and dry etching characteristics, and canreadily form a resist pattern excellent in sensitivity, resolution,flatness, heat resistance and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

By the present invention, a polymer having monomer units formed bycyclopolymerization of a fluorinated diene represented by the followingformula (1) (hereinafter referred to as the fluorinated diene (1), thesame applies hereinafter), and a process for its production can beprovided:

CF₂═CFCH₂CHQ-CH₂CR¹═CHR²  (1)

wherein each of R¹ and R² which are independent of each other, is ahydrogen atom or an alkyl group having at most 12 carbon atoms. Thealkyl group having at most 12 carbon atoms may have not only a straightor branched aliphatic hydrocarbon but also an alicyclic hydrocarbongroup. The alicyclic hydrocarbon group is preferably a hydrocarbon grouphaving at least one cyclic structure, and it includes, for example, thefollowing monocyclic saturated hydrocarbon groups, such as a cyclobutylgroup, a cycloheptyl group and a cyclohexyl group, bicyclic saturatedhydrocarbon groups such as a 4-cyclohexylcyclohexyl group, polycyclicsaturated hydrocarbon groups such as 1-decahydronaphthyl group and2-decahydronaphthyl group, crosslinked cyclic saturated hydrocarbongroups such as a 1-norbornyl group and a 1-adamantyl group, andspirohydrocarbon groups such as a spiro[3,4]octyl group:

Each of the above R¹ and R² is preferably a hydrogen atom, a methylgroup or an alicyclic hydrocarbon groups having at most 6 carbon atoms,particularly preferably a hydrogen atom or a methyl group. Both R¹ andR² are most preferably hydrogen atoms.

Q is (CH₂)_(a)C(CF₃)_(b)(R³)_(c)OR⁴ (wherein a is an integer of from 0to 3, and is preferably 0 or 1. b and c are integers of from 0 to 2satisfying b+c=2, R³ is a hydrogen atom or a methyl group, R⁴ is analkyl group or a fluorinated alkyl group having at most 20 carbon atomswhich may have an etheric oxygen atom, an alkoxycarbonyl group having atmost 6 carbon atoms, or CH₂R⁵ (wherein R⁵ is an alkoxycarbonyl grouphaving at most 6 carbon atoms)), or (CH₂)_(d)COOR⁶ (wherein d is 0 or 1,and R⁶ is a hydrogen atom, or an alkyl group or a fluorinated alkylgroup having at most 20 carbon atoms).

The alkyl group or the fluorinated alkyl group having at most 20 carbonatoms which may have an etheric oxygen atom, may have not only astraight or branched aliphatic hydrocarbon group but also an alicyclichydrocarbon group. As the alicyclic hydrocarbon group, the same group asmentioned above may be used, or may have an etheric oxygen atom in itscyclic structure. The specific examples may be a methyl group, atrifluoromethyl group, t-C₄H₉, CH₂OCH₃, CH₂OC₂H₅, CH₂OCH₂CF₃, a2-tetrahydropyranyl group and the following groups (in order to makeclear their bonding position, they are shown in the form of —OR⁴).

The alkoxycarbonyl group having at most 6 carbon atoms and CH₂R⁵ may berepresented by COOR⁷ and CH₂COOR⁷ (R⁷ is an alkyl group having at most 5carbon atoms), respectively, and as specific examples, COO(t-C₄H₉) andCH₂COO(t-C₄H₉) may be mentioned, respectively.

The alkyl group having at most 20 carbon atoms or the fluorinated alkylgroup in R⁶ may have an alicyclic hydrocarbon atom, and preferably hasat most 12 carbon atoms. As the alicyclic hydrocarbon group, the samegroup as mentioned above may be used, and the following groups mayspecifically be mentioned (in order to make clear their bondingposition, they are shown in the form of —OR⁶).

R⁶ is preferably a hydrogen atom or an alkyl group having at most 4carbon atoms, particularly preferably a hydrogen atom or a t-butylgroup.

As the fluoropolymer (A) of the present invention, it is preferred thatin the above formula (1), each of R¹ and R² which are independent ofeach other, is a hydrogen atom, a methyl group or an alicyclichydrocarbon group having at most 6 carbon atoms, and Q is(CH₂)_(a)C(CF₃)_(b)(R³)_(c)OR⁴ (wherein a is an integer of from 0 to 3,b and c are integers of from 0 to 2 satisfying b+c=2, R³ is a hydrogenatom or a methyl group, R⁴ is an alkyl group having at most 5 carbonatoms which may have an etheric oxygen atom, an alkoxycarbonyl grouphaving at most 6 carbon atoms, or CH₂R⁵ (wherein R⁵ is an alkoxycarbonylgroup having at most 6 carbon atoms)), or (CH₂)_(d)COOR⁶ (wherein d is 0or 1, and R⁶ is a hydrogen atom, or an alkyl group or a fluorinatedalkyl group having at most 20 carbon atoms). Further, in the above, R⁶is more preferably a hydrogen atom or an alkyl group having at most 5carbon atoms.

Further, the fluoropolymer (A) of the present invention is particularlypreferably a fluoropolymer having monomer units formed bycyclopolymerization of a fluorinated diene represented by the followingformula (2) or (3). a, b, c, d, R³, R⁴ and R⁶ are as mentioned above.

CF₂═CFCH₂CH((CH₂)_(a)C(CF₃)_(b)(R³)_(c)OR⁴)—CH₂CH═CH₂  (2)

CF₂═CFCH₂CH((CH₂)_(d)COOR⁶)—CH₂CH═CH₂  (3)

Such a fluorinated diene (1) can be polymerized under a relatively mildcondition, whereby a cyclized polymer having ether groups, ester groupsor carboxylic acid groups in side chains of the cyclic structure, can beobtained.

By the cyclopolymerization of the fluorinated diene (1), the followingmonomer units (a) to (c) are considered to be formed, and from theresults of the spectroscopic analyses, etc., the fluoropolymer (A) isconsidered to be a polymer having a structure comprising at least onetype of monomer units selected from the group consisting of monomerunits (a), monomer units (b) and monomer units (c). Further, the mainchain of the fluoropolymer (A) is meant for a carbon chain constitutedby carbon atoms which constitute polymerizable unsaturated bonds (in thecase of the fluorinated diene (1), the four carbon atoms whichconstitute polymerizable unsaturated double bonds).

The fluoropolymer (A) contains monomer units formed bycyclopolymerization of the fluorinated diene (1), as essentialcomponents, but may further contain monomer units derived from otherradical polymerizable monomers (hereinafter referred to as othermonomers) within a range not to impair the characteristics. Theproportion of such other monomer units is preferably at most 50 mol %,particularly preferably at: most 15 mol %.

Such other monomers may, for example, be an α-olefin such as ethylene,propylene or isobutylene, a fluorinated olefin such astetrafluoroethylene or hexafluoropropylene, a fluorinated cyclic monomersuch as perfluoro(2,2-dimethyl-1,3-dioxol), a cyclopolymerizableperfluorodiene or hydrofluorodiene, such as perfluoro(butenyl vinylether), an acryl ester such as methyl acrylate or ethyl methacrylate, avinyl ester such as vinyl acetate, vinyl benzoate or vinyl adamantate, avinyl ether such as ethyl vinyl ether or cyclohexyl vinyl ether, acyclic olefin such as cyclohexene, norbornene or norbornadiene, maleicanhydride, or vinyl chloride.

The fluoropolymer (A) of the present invention can be obtained byhomopolymerizing the fluorinated diene (1) or copolymerizing it with thecopolymerizable other monomer in the presence of a polymerizationinitiating source. The polymerization initiating source is notparticularly limited so long as it is capable of letting thepolymerization reaction proceed radically, and it may, for example, be aradical-generating agent, light or ionizing radiation. Aradical-generating agent is particularly preferred, and it may, forexample, be a peroxide, an azo compound or a persulfate. Among them, thefollowing peroxides are preferred.

C₆H₅—C(O)O—OC(O)—C₆H₅

C₆F₅—C(O)O—OC(O)—C₆F₅

C₃F₇—C(O)O—OC(O)—C₃F₇

(CH₃)₃C—C(O)O—OC(O)—C(CH₃)₃

(CH₃)₂CH—C(O)O—OC(O)—CH(CH₃)₂

(CH₃)₃C—C₆H₁₀—C(O)O—OC(O)—C₆H₁₀—C(CH₃)₃

(CH₃)₃C—O—C(O)O—OC(O)—O—C(CH₃)₃,

(CH₃)₂CH—O—C(O)O—OC(O)—O—CH(CH₃)₂,

(CH₃)₃C—C₆H₁₀—O—C(O)O—OC(O)—O—C₆H₁₀—C(CH₃)₃.

Here, C₆H₅ represents a phenyl group, C₆F₅ a pentafluorophenyl group andC₆H₁₀ a cyclohexylene group.

The polymerization method is also not particularly limited, and it may,for example, be so-called bulk polymerization wherein a monomer issubjected to polymerization as it is, solution polymerization which iscarried out in a fluorohydrocarbon, a chlorohydrocarbon, afluorochlorohydrocarbon, an alcohol, a hydrocarbon or other organicsolvent, in which the fluorinated diene (1) and the other monomer can bedissolved or dispersed, suspension polymerization which is carried outin an aqueous medium in the absence or presence of a suitable organicsolvent, or emulsion polymerization which is carried out in an aqueousmedium in the presence of an emulsifier.

The polymerization temperature and pressure are also not particularlylimited, but it is preferred to properly set them taking intoconsideration various factors such as the boiling point of the monomer,the heating source, removal of the polymerization heat, etc. Forexample, suitable temperature setting can be carried out between 0° C.to 200° C., and practically suitable temperature setting can be carriedout within a range of from room temperature to 100° C. Further, thepolymerization pressure may be a reduced pressure or an elevatedpressure, and practically, the polymerization can properly be carriedout within a range of from normal pressure to about 100 atom, preferablyfrom normal pressure to 10 atom.

Further, the present invention provides a fluorinated diene representedby the following formula (2) or (3) which can form suitable polymersamong the fluoropolymer (A):

CF₂═CFCH₂CH((CH₂)_(a)C(CF₃)_(b)(R³)_(c)OR⁴)—CH₂CH═CH₂  (2)

wherein a, b, c are as defined above, and it is preferred that b is 1and c is 1, or b is 2 and c is 0. R³ and R⁴ are as defined above.

CF₂═CFCH₂CH((CH₂)_(d)COOR⁶)—CH₂CH═CH₂  (3)

wherein d and R⁶ are as defined above.

The following compounds may be mentioned as specific examples of thefluorinated diene (2) and the fluorinated diene (3) of the presentinvention, but the present invention is not limited thereto.

Further, the present invention provides a resist composition comprisinga fluoropolymer (A), an acid-generating compound (B) which generates anacid under irradiation with light and an organic solvent (C).

The acid-generating compound (B) which generates an acid underirradiation with light of the present invention generates an acid underirradiation with light. By the acid thus generated, a blocked acidicgroup which exists in the fluoropolymer (A), is cleaved (deblocked). Asa result, the exposed portions of the resist film will become readilysoluble by an alkali developer, whereby a positive resist pattern willbe formed by the alkali developer. As such an acid-generating compound(B) which generates an acid under irradiation with light, it is possibleto employ an acid-generating compound which is commonly used for achemical amplification type resist material. Namely, an onium salt, ahalogenated compound, a diazoketone compound, a sulfone compound or asulfonic acid compound may, for example, be mentioned. The followingcompounds may be mentioned as examples of such an acid-generatingcompound (B).

The onium salt may, for example, be an iodonium salt, a sulfonium salt,a phosphonium salt, a diazonium salt or a pyridinium salt. Specificexamples of a preferred onium salt include diphenyliodonium triflate,diphenyliodoniumpyrene sulfonate, diphenyliodoniumdodecylbenzenesulfonate, bis(4-tert-butylphenyl)iodonium triflate,bis(4-tert-butylphenyl)iodonium dodecylbenzene sulfonate,triphenylsulfonium triflate, triphenylsulfonium nonanate,triphenylsulfoniumperfluorooctane sulfonate, triphenylsulfoniumhexafluoroantimonate, 1-(naphthylacetomethyl)thiolanium triflate,cyclohexylmethyl(2-oxocyclohexyl)sulfonium triflate,dicyclohexyl(2-oxocyclohexyl)sulfonium triflate,dimethyl(4-hydroxynaphthyl)sulfonium tosylate,dimethyl(4-hydroxynaphthyl)sulfonium dodecylbenzene sulfonate,dimethyl(4-hydroxynaphthyl)sulfonium naphthalene sulfonate,triphenylsulfonium camphor sulfonate or(4-hydroxyphenyl)benzylmethylsulfonium toluene sulfonate.

The halogenated compound may, for example, be a haloalkylgroup-containing hydrocarbon compound or a haloalkyl group-containingheterocyclic compound. Specifically, it may, for example, be a(trichloromethyl)-s-triazine derivative such asphenyl-bis(trichloromethyl)-s-triazine,methoxyphenyl-bis(trichloromethyl)-s-triazine ornaphthyl-bis(trichloromethyl)-s-triazine, or1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane.

The sulfone compound may, for example, be β-ketosulfone,β-sulfonylsulfone or an α-diazo compound of such a compound.Specifically, it may, for example, be 4-trisphenacylsulfone,mesitylphenacylsulfone or bis(phenylsulfonyl)methane. The sulfonic acidcompound may, for example, be an alkylsulfonic acid ester, analkylsulfonic acid imide, a haloalkylsulfonic acid ester, anarylsulfonic acid ester or an iminosulfonate. Specifically, it may, forexample, be benzoine tosylate or 1,8-naphthalene dicarboxylic acid imidetriflate. In the present invention, such acid-generating compounds (B)may be used alone or in combination as a mixture of two or more of them.

The organic solvent (C) of the present invention is not particularlylimited so long as it is capable of dissolving both components (A) and(B). It may, for example, be an alcohol such as methyl alcohol or ethylalcohol, a ketone such as acetone, methylisobutyl ketone orcyclohexanone, an acetate such as ethyl acetate or butyl acetate, anaromatic hydrocarbon such as toluene or xylene, a glycol monoalkyl ethersuch as propylene glycol monomethyl ether or propylene glycol monoethylether, or a glycol monoalkyl ether ester such as propylene glycolmonomethyl ether acetate or carbitol acetate.

The proportions of the respective components in the resist compositionof the present invention are usually such that the acid-generatingcompound (B) is from 0.1 to 20 parts by mass and the organic solvent (C)is from 50 to 2,000 parts by mass, per 100 parts by mass of the isfluoropolymer (A). Preferably, the acid-generating compound (B) is from0.1 to 10 parts by mass and the organic solvent (C) is from 100 to 1,000parts by mass, per 100 parts by mass of the fluoropolymer (A).

If the amount of the acid-generating compound (B) is at least 0.1 partby mass, a sufficient sensitivity and developability can be provided,and if it is at most 10 parts by mass, a sufficient transparency toradiation is retained, whereby a more accurate resist pattern can beobtained.

In the resist composition of the present invention, an acid-cleavableadditive to improve the pattern contrast, a surfactant to improve thecoating property, a nitrogen-containing basic compound to adjust theacid-generating pattern, an adhesion-assisting agent to improve theadhesion to a substrate or a storage stabilizer to enhance the storagestability of the composition, may be optionally incorporated. Further,the resist composition of the present invention is preferably employedin such a manner that the respective components are uniformly mixed,followed by filtration by means of a filter of from 0.1 to 2 μm.

The resist composition of the present invention is coated on a substratesuch as a silicon wafer, followed by drying to form a resist film. Asthe coating method, spin coating, cast coating or roll coating may, forexample, be employed. The formed resist film will be irradiated withlight through a mask having a pattern drawn thereon, followed bydevelopment treatment to form the pattern.

The light beams for the irradiation may, for example, be ultravioletrays such as g-line having a wavelength of 436 nm or i-line having awavelength of 365 nm, or far ultraviolet rays or vacuum ultravioletrays, such as KrF excimer laser having a wavelength of 248 nm, ArFexcimer laser having a wavelength of 193 nm or F₂ excimer laser having awavelength of 157 nm. The resist composition of the present invention isa resist composition useful particularly for an application whereultraviolet rays having a wavelength of at most 250 nm, especiallyultraviolet rays having a wavelength of at most 200 nm (such as ArFexcimer laser or F₂ excimer laser), are used as the light source.

As the development treatment solution, various alkali aqueous solutionsare employed. As such an alkali material, sodium hydroxide, potassiumhydroxide, ammonium hydroxide, tetramethylammonium hydroxide ortriethylamine may, for example, be mentioned.

EXAMPLES

Now, the present invention will be described in detail with reference toExamples, but it should be understood that the present invention is byno means restricted thereto.

Abbreviations used in the following Examples are as follows.

THF: tetrahydrofuran, AIBN: azobisisobutyronitrile, BPO: benzoylperoxide, PSt: polystyrene, R225: dichloropentafluoropropane (solvent),IPP: diisopropylperoxydicarbonate, Cy: cyclohexyl group and AdM:2-methyladamantan-2-yl group (as follows).

Example 1 Preparation of CF₂═CFCH₂CH(CH₂C(CF₃)₂OCH₂OCH₃)CH₂CH═CH₂

Into a 200 mL glass reactor, 118 g of CF₂ClCFClI and 1.1 g of AIBN wereput and heated to 75° C. 75.8 g of CH₂═CHCH₂C(CF₃)₂OCH₂OCH₃ was dropwiseadded thereto over a period of 1 hour. After completion of the dropwiseaddition, the mixture was stirred at 75° C. for 7 hours, and distilledunder reduced pressure to obtain 144 g of CF₂ClCFClCH₂CHI(CH₂C(CF₃)₂OCH₂OCH₃) (80-85° C./0.16 kPa).

Into a 2 L glass reactor, 144 g of the above preparedCF₂ClCFClCH₂CHI(CH₂C(CF₃)₂OCH₂OCH₃) and 550 mL of dehydrated THF wereput and cooled to −75° C. 220 mL of a 2M-THF solution of CH₂═CHCH₂MgClwas dropwise added thereto over a period of 2 hours.

After stirring at −75° C. for 3 hours, 400 mL of an aqueous saturatedammonium chloride solution was added thereto, and the temperature wasraised to room temperature. The reaction solution was subjected toliquid separation, and the organic layer was concentrated by anevaporator and then distilled under reduced pressure to obtain 66.3 g ofCF₂ClCFClCH₂CH(CH₂C(CF₃)₂OCH₂OCH₃)CH₂CH═CH₂ (54-56° C./0.08 kPa). Into a200 mL glass reactor, 30 g of zinc and 100 g of water were put andheated to 85° C. Then, 66.3 g of the above preparedCF₂ClCFClCH₂CH(CH₂C(CF₃)₂OCH₂OCH₃)CH₂CH═CH₂ was dropwise added thereto,followed by stirring for 24 hours. The reaction solution was filtratedand subjected to liquid separation, and then distilled under reducedpressure to obtain 23.6 g of CF₂═CFCH₂CH(CH₂C(CF₃)₂OCH₂OCH₃)CH₂CH═CH₂(54-56° C./0.5 kPa).

NMR Spectra

¹H-NMR (399.8 MHz, solvent: CDCl₃, standard: tetramethylsilane) δ (ppm):1.92 (m, 2H), 2.33 (m, 5H), 3.44 (s, 3H), 3.74 (br, 1H), 4.95 (m, 2H),5.12 (m, 2H), 5.75 (m, 1H).

¹⁹F-NMR (376.2 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −77.3 (m,3F), −77.8 (m, 3F), −92.9 (m, 1F), −104.2 (dd, J=33.24, 85.97 Hz, 1F),−123.5 (dd, J=85.97, 113.9 Hz, 1F), −171.9 (m, 1F).

Example 2 Preparation of CF₂═CFCH₂CH(CH₂C(CF₃)₂OCH₂OCH₃)CH₂C(Cy)=CH₂

CF₂═CFCH₂CH(CH₂C(CF₃)₂OCH₂OCH₃)CH₂C(Cy)=CH₂ can be obtained by carryingout the preparation in the same manner as in Example 1 except that inExample 1, 220 mL of a 2M-THF solution of CH₂═C(Cy)CH₂MgCl is usedinstead of 220 mL of a 2M-THF solution of CH₂═CHCH₂MgCl.

Example 3 Preparation of CF₂═CFCH₂CH(CH₂OCH₂OCH₃)CH₂CH═CH₂

60 g of CF₂═CFCH₂CH(CH₂OCH₂OCH₃)CH₂CH═CH₂ (65-67° C./0.5 kPa) wasobtained by carrying out the preparation in the same manner as inExample 1 except that in Example 1, 557 g of CF₂ClCFClI and 4.5 g ofAIBN were used, 141.2 g of CH₂═CHCH₂OCH₂OCH₃ was used instead of 75.8 gof CH₂═CHCH₂C(CF₃)₂OCH₂OCH₃, and 1 L of dehydrated THF and 500 mL of a2M-THF solution were used.

NMR Spectra

¹H-NMR (399.8 MHz, solvent: CDCl₃, standard: tetramethylsilane) δ (ppm):1.78 (m, H), 1.96 (m, 1H), 2.18 (m, 2H), 2.37 (m, 2H), 3.44 (s, 3H),3.61 (m, 2H), 4.95 (m, 2H), 5.10 (m, 2H), 0.79 (m, 1H).

¹⁹F-NMR (376.2 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −104.5(dd, J=32.24, 85.96 Hz, 1F), −123.8 (ddt, J=4.29, 85.96, 113.9 Hz, 1F),−171.9 (ddt, J=23.6, 32.24, 113.9 Hz, 1F).

Preparation Example 1 Preparation of CF₂═CFCH₂CH(CH₂OH)CH₂CH═CH₂

40 g of CF₂═CFCH₂CH(CH₂OCH₂C)CH₃)CH₂CH═CH₂ obtained in Example 3 and 100mL of methanol were put into a 300 mL glass reactor, and a catalyticamount of concentrated hydrochloric acid was added thereto, followed byheating at 60° C. for 19 hours. The reaction solution was cooled to roomtemperature, and 30 mL of water was added to carry out liquidseparation. The organic layer was further washed with 50 mL of water andsubjected to precision distillation to obtain 35.3 g ofCF₂═CFCH₂CH(CH₂OH)CH₂CH═CH₂ (59-60° C./0.5 kPa).

NMR Spectra

¹H-NMR (399.8 MHz, solvent: CDCl₃, standard: tetramethylsilane) δ (ppm):1.78 (m, 1H), 1.96 (m, 1H), 2.18 (m, 2H), 2.37 (m, 2H), 3.61 (m, 2H),5.10 (m, 2H), 5.79 (m, 1H).

¹⁹F-NMR (376.2 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −104.5(dd, J=32.24, 85.96 Hz, 1F), −123.8 (ddt, J=4.29, 85.96, 113.9 Hz, 1F),−171.9 (ddt, J=23.6, 32.24, 113.9 Hz, 1F).

Example 4 Preparation of CF₂═CFCH₂C(C(CH₃)(CF₃)OCH₂OCH₃)CH₂CH═CH₂

25 g of CF₂═CFCH₂C(C(CH₃)(CF₃)OCH₂OCH₃)CH₂CH═CH₂ (45-47° C./0.15 kPa)was obtained by carrying out the preparation in the same manner as inExample 1 except that in Example 1, 385 g of CF₂ClCFClI and 28.1 g ofAIBN were used, 178 g of CH₂═CHC(CH₃)(CF₃)OCH₂OCH₃ was used instead of75.8 g of CH₂═CHCH₂C(CF₃)₂OCH₂OCH₃, and 1 L of dehydrated THF and 660 mLof a 2M-THF solution were used.

NMR Spectra

¹H-NMR (399.8 MHz, solvent: CDCl₃, standard: tetramethylsilane) δ (ppm):1.38 (m, 3H), 2.19 (m, 4H), 2.44 (m, 1H), 2.67 (m, 1H), 3.44 (s, 3H),4.95 (m, 2H), 5.12 (m, 2H), 5.82 (m, 1H).

¹⁹F-NMR (376.2 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −78.5 (d,J=62.3, 3F), 104.2 (dddd, J=4.29, 32.2, 49.4, 85.9 Hz, 1F), −123.0 (dd,J=38.7, 83.8 Hz, 1F), −173.1 (m, 1F).

Preparation Example 2 Preparation of CF₂═CFCH₂C(C(CH₃)(CF₃)OH)CH₂CH═CH₂

10.7 g of CF₂═CFCH₂C(C(CH₃)(CF₃)OH)CH₂CH═CH₂ (40-42° C./0.15 kPa) wasobtained by carrying out the preparation in the same manner as inPreparation Example 1 except that in Preparation Example 1, 25 g ofCF₂═CFCH₂C(C(CH₃)(CF₃)OCH₂OCH₃)CH₂CH═CH₂ obtained in Example 3 was usedinstead of 40 g of CF₂═CFCH₂CH(CH₂OCH₂OCH₃)CH₂CH═CH₂, and 60 mL ofmethanol was used.

NMR Spectra

¹H-NMR (399.8 MHz, solvent: CDCl₃, standard: tetramethylsilane) δ (ppm):1.38 (m, 3H), 2.19 (m, 4H), 2.44 (m, 1H), 2.67 (m, 1H), 5.12 (m, 2H),5.82 (m, 1H).

¹⁹F-NMR (376.2 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −78.5 (d,J=62.3, 3F), −104.2 (dddd, J=4.29, 32.2, 49.4, 85.9 Hz, 1F), −123.0 (dd,J=38.7, 83.8 Hz, 1F), −173.1 (m, 1F).

Example 5 Preparation of CF₂═CFCH₂C(C(O)OC(CH₃)₃)CH₂CH═CH₂

Into a 200 mL glass reactor, 91.8 g of CF₂ClCFClI and 0.75 g of BPO wereput and heated to 85° C. 30 g of CH₂═CHC(O)OC(CH₃)₃ was dropwise addedthereto over a period of 0.5 hour. After completion of the dropwiseaddition, the mixture was stirred at 85° C. for 7 hours, and thendistilled under reduced pressure to obtain 56 g ofCF₂ClCFClCH₂CHI(C(O)OC(CH₃)₃) (80-85° C./0.2 KPa).

Into a 1 L glass reactor, 50 g of the above preparedCF₂ClCFClCH₂CHI(C(O)OC(CH₃)₃) and 360 mL of dehydrated THF were put andcooled to −75° C. 80 mL of a 1.6 M hexane solution of n-BuLi wasdropwise added thereto over a period of 1.5 hours. After stirring at−75° C. for 1 hour, a solution prepared by diluting 22 g of allylbromide with 50 mL of THF, was dropwise added thereto over a period of 1hour. After further stirring for 3 hours, 200 mL of an aqueous saturatedammonium chloride solution was added thereto, and the temperature wasraised to room temperature. The reaction solution was subjected toliquid separation, and the organic layer was concentrated by anevaporator and distilled under reduced pressure to obtain 22 g ofCF₂ClCFClCH₂C(C(O)OC(CH₃)₃)CH₂CH═CH₂ (70-75° C./0.2 kPa). Into a 200 mLglass reactor, 22 g of zinc and 80 g of water were put and heated to 90°C. 22 g of the above prepared CF₂ClCFClCH₂C(C(O)OC(CH₃)₃)CH₂CH═CH₂ wasdropwise added thereto and then stirred for 10 hours. The reactionsolution was filtrated, and the organic layer was distilled underreduced pressure to obtain 2.5 g of CF₂═CFCH₂C(C(O)OC(CH₃)₃)CH₂CH═CH₂(50-55° C./0.8 kPa).

NMR Spectra

¹H-NMR (399.8 MHz, solvent: CDCl₃, standard: tetramethylsilane) δ (ppm):1.37 (s, 9H), 2.39 (m, 5H), 5.02 (m, 2H), 5.65 (m, 1H)

¹⁹F-NMR (376.2 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −104.7(dd, J=32.7, 85.0 Hz, 1F), −123.5 (m, 1F), −171.4 (m, 1F).

Example 6 Preparation of CF₂═CFCH₂C(C(O)O(AdM))CH₂CH═CH₂

CF₂═CFCH₂C(C(O)O(AdM))CH₂CH═CH₂ can be obtained by carrying out thepreparation in the same manner as in Example 5 except that in Example 5,55 g of CH₂═CHC(O)O(AdM) is used instead of 30 g of CH₂═CHC(O)OC(CH₃)₃.

Example 7

5.6 g of the monomer obtained in Example 1 was charged into a pressureresistant reactor made of glass and having an internal capacity of 30mL. Then, 0.14 g of perfluorobenzoyl peroxide was added as apolymerization initiator. The interior of the system wasfreezed-deaerated, and then the reactor was sealed, followed bypolymerization for 18 hours in a constant temperature shaking bath (70°C.). After the polymerization, the reaction solution was dropped intohexane to reprecipitate the polymer, followed by vacuum drying at 105°C. for 20 hours. As a result, 2.62 g of a non-crystalline polymer havinga fluorinated cyclic structure in its main chain (hereinafter referredto as polymer 1A), was obtained. The molecular weight measured by GPCemploying THF as a solvent and calculated as PSt, was such that thenumber average molecular weight (Mn) was 9,200, and the weight averagemolecular weight (Mw) was 17,100, and Mw/Mn=1.85. Tg measured by thedifferential scanning calorimetry (DSC) was 104° C., and the polymer wasa white powder at room temperature. The polymer obtained was soluble inacetone, THF, ethyl acetate and methanol and was insoluble in R225,perfluoro(2-butyltetrahydrofuran) and perfluoro-n-octane.

By ¹⁹F-NMR and ¹H-NMR, it was confirmed to be a cyclized polymer havingthe following monomer units of (d), (e) and (f).

Example 8

1.25 g of the monomer obtained in Example 3, 5.01 g of the monomerobtained in Preparation Example 1 and 9.4 g of methyl acetate werecharged into a pressure resistant reactor made of glass and having aninternal capacity of 30 mL. Then, 0.23 g of perfluorobenzoyl peroxidewas added as a polymerization initiator. The interior of the system wasfreeze-deaerated, and then the reactor was sealed, followed bypolymerization for 18 hours in a constant temperature shaking bath (70°C.). After the polymerization, the reaction solution was dropped intohexane to reprecipitate the polymer, followed by vacuum drying at 106°C. for 16 hours. As a result, 1.05 g of a non-crystalline polymer havinga fluorinated cyclic structure in its main chain (hereinafter referredto as polymer 2A), was obtained. The molecular weight measured by GPCemploying THF as a solvent and calculated as PSt, was such that thenumber average molecular weight (Mn) was 5,100, and the weight averagemolecular weight (Mw) was 10,200, and Mw/Mn=2.02. Tg measured by thedifferential scanning calorimetry (DSC) was 98° C., and the polymer wasa white powder at room temperature. The polymer obtained was soluble inacetone, THF and methanol and was insoluble in R225,perfluoro(2-butyltetrahydrofuran) and perfluoro-n-octane.

Example 9

2.34 g of the monomer obtained in Example 4, 9.36 g of the monomerobtained in Preparation Example 2 and 22.2 g of methyl acetate werecharged into a pressure resistant reactor made of glass and having aninternal capacity of 50 mL. Then, 0.408 g of IPP was added as apolymerization initiator. The interior of the system wasfreeze-deaerated, and then the reactor was sealed, followed bypolymerization for 18 hours in a constant temperature shaking bath (40°C.). After the polymerization, the reaction solution was dropped intohexane to reprecipitate the polymer, followed by vacuum drying at 125°C. for 10 hours. As a result, 1.93 g of a non-crystalline polymer havinga fluorinated cyclic structure in its main chain (hereinafter referredto as polymer 3A), was obtained. The molecular weight measured by GPCemploying THF as a solvent and calculated as PSt, was such that thenumber average molecular weight (Mn) was 16,900, and the weight averagemolecular weight (Mw) was 34,700, and Mw/Mn=2.05. Tg measured by thedifferential scanning calorimetry (DSC) was 133° C., and the polymer wasa white powder at room temperature. The polymer obtained was soluble inacetone, THF, ethyl acetate, methanol and 2-perfluorohexyl ethanol, andwas insoluble in R225, perfluoro(2-butyltetrahydrofuran) andperfluoro-n-octane.

Example 10

2 g of the monomer obtained in Example 5 was charged into a glass tubehaving an inner diameter of 10 mm and a length of 300 mm. Then, 40 mg ofperfluorobenzoyl peroxide was added as a polymerization initiator. Theinterior of the system was freeze-deaerated, and then the tube wassealed, followed by polymerization for 20 hours in a constanttemperature shaking bath (70° C.). After the polymerization, thereaction solution was dropped into methanol to reprecipitate thepolymer, followed by vacuum drying at 130° C. for 20 hours. As a result,1.36 g of a non-crystalline polymer having a fluorinated cyclicstructure in its main chain (hereinafter referred to as polymer 4A), wasobtained. The molecular weight measured by GPC employing THF as asolvent and calculated as PSt, was such that the number averagemolecular weight (Mn) was 23,700, and the weight average molecularweight (Mw) was 71,800, and Mw/Mn=3.03. Tg measured by the differentialscanning calorimetry (DSC) was 90° C., and the polymer was a whitepowder at room temperature. The polymer obtained was soluble in acetone,THF, ethyl acetate, hexane, R225 and 2-perfluorohexyl ethanol, and wasinsoluble in methanol, perfluoro(2-butyltetrahydrofuran) andperfluoro-n-octane.

Example 11

5 g of the monomer obtained in Preparation Example 2 was charged into apressure resistant reactor made of glass and having an internal capacityof 30 mL. Then, 0.14 g of perfluorobenzoyl peroxide was added as apolymerization initiator. The interior of the system wasfreeze-deaerated, and then the reactor was sealed, followed bypolymerization for 18 hours in a constant temperature shaking bath (70°C.) After the polymerization, the reaction solution was dropped intohexane to reprecipitate the polymer, followed by vacuum drying at 105°C. for 20 hours. As a result, 2.1 g of a non-crystalline polymer havinga fluorinated cyclic structure in its main chain, was obtained. Byemploying 2.1 g of the obtained polymer, a methanol solution of sodiumhydroxide, and (1-adamantyl methyl)chloromethyl ether, it is possible toobtain a polymer having some hydroxyl groups of the polymeradamantylmethoxymethylated.

Example 12

30 g of CF₂═CFCH₂CH(CH₂C(CF₃)₂OCH₂OCH₃)CH₂CH═CH₂ obtained in Example 1and 100 mL of methanol were put into a 200 mL glass reactor, and acatalytic amount of concentrated hydrochloric acid was added thereto,followed by heating at 60° C. for 20 hours. The reaction solution wascooled to room temperature, and 30 mL of water was added to carry outliquid separation. The organic layer was further washed with 50 mL ofwater and subjected to precision distillation to obtain 25 g ofCF₂═CFCH₂CH(CH₂C(CF₃)₂OH)CH₂CH═(H₂. 12 g of the monomer obtained wascharged into a pressure resistant reactor made of glass and having aninternal capacity of 50 mL. Then, 0.45 g of perfluorobenzoyl peroxidewas added as a polymerization initiator. The interior of the system wasfreeze-deaerated, and then the reactor was sealed, followed bypolymerization for 18 hours in a constant temperature shaking bath (70°C.). After the polymerization, the reaction solution was dropped intohexane to reprecipitate the polymer, followed by vacuum drying at 100°C. for 22 hours to obtain 10.6 g of a polymer. 2 g of the obtainedpolymer, 1.25 g of a 7.7 wt % methanol solution of sodium hydroxide and40 mL of methanol were put and stirred at 45° C. for 18 hours. Thereaction solution was concentrated by an evaporator and then dissolvedin 60 mL of dehydrated THF. Then, 0.472 g of CH₂BrCOO(t-C₄H₉) was addedthereto, and the mixture was stirred at room temperature for 66 hoursand at 65° C. for 42 hours. The reaction solution was subjected tofiltration through celite, and concentrated by an evaporator. Theconcentrated product was dissolved in R225 and washed with water,followed by liquid separation. The R225 layer was dropped into hexane toreprecipitate the polymer, followed by vacuum drying at 90° C. for 14hours. As a result, 1.97 g of a non-crystalline polymer having afluorinated cyclic structure in its main chain was obtained. By analysesof ¹⁹F-NMR and ¹H-NMR, it was confirmed that 28 mol % of the hydroxylgroup was blocked with —CH₂COO(t-C₄H₉). Its molecular weight measured byGPC employing THF as a solvent and calculated as PSt, was such that thenumber average molecular weight (Mn) was 9,100, and the weight averagemolecular weight (Mw) was 16,300, and Mw/Mn=1.78. Tg measured by thedifferential scanning calorimetry (DSC) was 89° C., and the polymer wasa white powder at room temperature. The polymer obtained was soluble inacetone, THF, methanol and R225.

Examples 13 to 16

1 g of each of polymers 1A to 4A prepared in Examples 7 to 10 and 0.05 gof trimethylsulfonium triflate were dissolved in 10 g of propyleneglycol monomethyl ether acetate and filtered through a filter made ofPTFE and filter having a pore diameter of 0.2 μm to produce a resistcomposition.

The above resist composition was spin-coated on a silicon substratetreated with hexamethyldisilazane, followed by heat treatment at 80° C.for 2 minutes to form a resist film having a thickness of 0.3 μm. In anexposure test apparatus flushed with nitrogen, the substrate having theabove resist film formed, was placed, and a mask having a pattern drawnby chrome on a quartz plate, was put thereon in close contact therewith.KrF excimer laser beams were irradiated through the mask, whereupon,after exposure at 100° C. for 2 minutes, baking was carried out. Thedevelopment was carried out at 23° C. for 1 minute with a tetramethylammonium hydroxide aqueous solution (2.38 mass %), followed by washingwith pure water for 1 minute. The light transmittance of the resist filmand the development test results are shown in Table 1.

TABLE 1 Transmittance Line and of light of space width Polymer 157 nm(%) (1/1) (μm) Ex. 13 1A 55 0.18 Ex. 14 2A 45 0.19 Ex. 15 3A 50 0.19 EX.16 4A 30 0.20

INDUSTRIAL APPLICABILITY

The fluoropolymer of the present invention is applicable to ion exchangeresins, ion exchange membranes, fuel cells, various cell materials,optical fibers, electronic members, transparent film materials,agricultural polyvinyl chloride films, adhesives, fiber materials,weather-resistant coating materials or the like, in addition to the useas a base polymer for photoresists.

The entire disclosures of Japanese Patent Application No. 2003-284156filed on Jul. 31, 2003 and Japanese Patent Application No. 2004-088337filed on Mar. 25, 2004 including specifications, claims and summariesare incorporated herein by reference in their entireties.

1-3. (canceled)
 4. A fluorinated diene represented by the followingformula (3):CF₂═CFCH₂CH((CH₂)_(d)COOR⁶)—CH₂CH═CH₂  (3) wherein d is 0 or 1, and R⁶is a hydrogen atom, or an alkyl group or a fluorinated alkyl grouphaving at most 20 carbon atoms.
 5. (canceled)
 6. The fluorinated dieneaccording to claim 4, wherein d is
 0. 7. The fluorinated diene accordingto claim 4, wherein d is
 1. 8. The fluorinated diene according to claim4, wherein R⁶ is a hydrogen atom.
 9. The fluorinated diene according toclaim 4, wherein R⁶ is an alkyl group.
 10. The fluorinated dieneaccording to claim 4, wherein R⁶ is a fluorinated alkyl group having atmost 20 carbon atoms.